EP0213401A2 - Process for the polymerization of isobutylene - Google Patents
Process for the polymerization of isobutylene Download PDFInfo
- Publication number
- EP0213401A2 EP0213401A2 EP86110542A EP86110542A EP0213401A2 EP 0213401 A2 EP0213401 A2 EP 0213401A2 EP 86110542 A EP86110542 A EP 86110542A EP 86110542 A EP86110542 A EP 86110542A EP 0213401 A2 EP0213401 A2 EP 0213401A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- isobutylene
- weight
- butene
- polymerization
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
- C08F10/10—Isobutene
Definitions
- the invention relates to a process for increasing sales in the production of polyisobutylene by polymerizing isobutylene in a polymerization zone in which a temperature between 0 and -13O ° C prevails, in the presence, in each case based on the isobutylene used, of O, O1 to 1, 0% by weight of boron trifluoride catalyst which contains less than 0.3% by volume of foreign constituents, 0.010 to 1.0% by weight of a molecular weight regulator, 30 to 90% by weight of a low-boiling solvent which is inert under the reaction conditions and - If necessary, polymerization accelerator in customary amounts, the solvent evaporated during the polymerization being continuously drawn off, liquefied and added to the polymerization zone again in the liquid state.
- isobutylene contains many impurities in the range of C2 to C7 hydrocarbons. Especially in the field of C4 hydrocarbons there are a large number of polymerization-active components that have to be separated by careful pressure distillation.
- the isobutylene obtained from isobutanol and contaminated with normal butenes, isobutyraldehyde and isobutyrether (purity approx. 88 - 99.8% by volume) is subjected to careful distillation here.
- a budimatisobutylene (purity 99.98 - 99 vol .-%) is formed, which is almost free of the aforementioned interfering components . While the concentration of the components which interfere with the isobutylene polymerization in the gap isobutylene can be between 0.2 and 12 vol.%, In budimatisobutylene this concentration is limited to ⁇ 2OOO vol. Ppm.
- the invention has for its object to find a method in which the above-mentioned disadvantages do not occur and an increase in sales can be achieved.
- the polymerization of isobutylene is carried out according to a known method at reaction temperatures between 0 and -16O ° C, preferably at temperatures between -5O ° C and -11O ° C.
- the process works without pressure.
- the Friedel-Crafts catalyst primarily boron trifluoride is used as the Friedel-Crafts catalyst in customary amounts of from 0.01 to 1.0 percent by weight, based on the isobutylene used.
- the so-called molecular weight regulators are used in customary amounts of from 1 to 50,000 ppm by weight, based on the isobutylene used.
- Such molecular weight regulators are, for example, the compounds diisobutylene, mercaptans, sulfides or polysulfides.
- the molecular weight regulators bring about a considerable increase in the reaction time and often also require an increase in the catalyst requirement.
- the polymerization of the isobutylene is carried out in the presence of 10 to 5,000 ppm by weight, based on the isobutylene used, of a polymerization accelerator. These substances accelerate the course of the reaction and reduce the amount of catalyst required. As a result of these additives, high-molecular polyisobutylenes are also formed, since chain-breaking influences are less effective.
- These are preferably primary or secondary alcohols with 1 to 10 carbon atoms, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, amyl alcohols, Cyclohexanol and benzyl alcohol. Phenols, carboxylic acids or mineral acids are also suitable.
- the polymerization of the isobutylene is carried out in the presence of 30 to 90% by weight, based on the isobutylene used, of a low-boiling solvent which is inert under the reaction conditions.
- Suitable solvents because of the favorable location of their boiling points are preferably methane, ethane, propane and especially ethylene, since the heat of polymerization of isobutylene can be removed in a simple manner by evaporating them under reaction conditions.
- the isobutylene is polymerized at the boiling point of the inert solvent. In the case of ethylene, the polymerization temperature is -1O4 ° C.
- the solvent evaporated during the polymerization is continuously drawn off, liquefied and returned to the polymerization zone in the liquid state.
- a content of 1.9 to 2.1, preferably 2.0,% by weight of butene-1 is kept constant in the monomeric isobutylene which is being polymerized.
- Butene-1 is available on the market in high purity (99.3% by weight of butene-1, 0.2% by weight of isobutene, 0.4% by weight of butane) and is used in this form.
- the butene-1 should contain a total of less than 50 ppm by weight of cis-butene-2 and trans-butene-2. The cis and trans isomers of butene-2 must be carefully separated by pressure distillation and dried with chlorine calcium.
- Butene-1 can be volumetrically added to the isobutylene. If certain butene-1 concentrations should already be present due to the production conditions, the content of butene-1 to 1.9 to 2.1 is preferably 2.0% by weight, either by adding butene-1 or by adding pure isobutene. adjust.
- the advantages achieved with the invention are to be seen in particular in that keeping approximately 2% by weight of the pure substance butene-1 in the isobutylene improves the polymerization behavior of the isobutylene, such as an increase in turnover, a smooth polymerization process, a reduced catalyst and regulator concentration.
- the working temperature was about 31O ° C.
- the catalyst solution is added to the polymerization solution.
- the reaction proceeds with the boiling and evaporation of the ethene and is complete after the reaction times given in the table.
- the isobutylene from experiment 4 is added to the butene-1 concentrations given in the table and investigated as described above.
- the butene-1 has the following purity: 99.7% by weight of butene-1, 0.2% by weight of butane (n- and isobutane), sum of cis- and trans-butene-2 50% by weight-ppm, Balance isobutylene.
- the mixture 98% by weight pure isobutylene (99.99% by weight isobutylene, ⁇ 100% by weight butane, ⁇ 50% by weight cis and trans-butene-2) and 2% by weight n- Butene-1 is the most optimal condition.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Umsatzsteigerung bei der Herstellung von Polyisobutylen durch Polymerisation von Isobutylen in einer Polymerisationszone, in der eine Temperatur zwischen O und -13O°C herrscht, in Gegenwart, jeweils bezogen auf das eingesetzte Isobutylen, von O,O1 bis 1,O Gew.-% Bortrifluoridkatalysator, der weniger als O,3 Vol.-% an Fremdbestandteilen enthält, O,OO1 bis 1,O Gew.-% eines Molekulargewichtsreglers, 3O bis 9O Gew.-% eines unter Reaktionsbedingungen inerten, niedrigsiedenden Lösungsmittels und - gegebenenfalls-Polymerisationsbeschleuniger in üblichen Mengen, wobei das bei der Polymerisation verdampfte Lösungsmittel kontinuierlich abgezogen, verflüssigt und im flüssigen Zustand erneut der Polymerisationszone zugefügt wird.The invention relates to a process for increasing sales in the production of polyisobutylene by polymerizing isobutylene in a polymerization zone in which a temperature between 0 and -13O ° C prevails, in the presence, in each case based on the isobutylene used, of O, O1 to 1, 0% by weight of boron trifluoride catalyst which contains less than 0.3% by volume of foreign constituents, 0.010 to 1.0% by weight of a molecular weight regulator, 30 to 90% by weight of a low-boiling solvent which is inert under the reaction conditions and - If necessary, polymerization accelerator in customary amounts, the solvent evaporated during the polymerization being continuously drawn off, liquefied and added to the polymerization zone again in the liquid state.
Bei derartigen Polymerisationsverfahren ist es erforderlich, in Gegenwart von Katalysatoren und Molekulargewichtsreglern sowie ggf. in Gegenwart von Polymerisationsbeschleunigern zu arbeiten, wobei letztere außer einer Erhöhung des Molekulargewichts des entstehenden Polymerisats eine Beschleunigung des Reaktionsablaufs und eine Verringerung der Katalysatormenge bewirken soll. Es ist ferner von technischem Interesse, die Polymerisation des Isobutylens bei festgelegten niedrigen Temperaturen durchzuführen, wo Vernetzungs- und Nebenreaktionen nicht vorhanden sind und gleichzeitig die Polymerisationswärme des Isobutylens abzuführen.In the case of such polymerization processes, it is necessary to work in the presence of catalysts and molecular weight regulators and, if appropriate, in the presence of polymerization accelerators, the latter being intended, in addition to increasing the molecular weight of the polymer formed, to accelerate the course of the reaction and to reduce the amount of catalyst. It is also of technical interest to carry out the polymerization of the isobutylene at specified low temperatures, where crosslinking and side reactions are not present, and at the same time to remove the heat of polymerization of the isobutylene.
Es ist bekannt, die Polymerisation des Isobutylens bzw. Isobutens zwischen O und -13O°C mit Friedel-Crafts-Verbindungen in Gegenwart von Molekulargewichtsreglern zu katalysieren und zur Beschleunigung der Reaktion in Anwesenheit von 1O bzw. 5OOO Gew.-ppm, bezogen auf das Isobutylen, eines Polymerisationsbeschleunigers zu arbeiten und zur Abführung der Reaktionswärme in Gegenwart eines niedrigsiedenden inerten Lösungsmittels, das unter Reaktionsbedingungen verdampft, zu polymerisieren (vgl. US-Patente 3 129 2O5, 2 9O6 798, 4 391 959, EP-A1-154164, DE-Patent 1O 99 171 und EP-B1-2553O). Bei den bekannten Verfahren wird das verdampfte Lösungsmittel in einem Kompressor verdichtet und in den Polymerisationsprozeß zurückgeführt.It is known to catalyze the polymerization of isobutylene or isobutene between 0 and -13O ° C with Friedel-Crafts compounds in the presence of molecular weight regulators and to accelerate the reaction in the presence of 1O or 5OOO ppm by weight, based on the Isobutylene, a polymerization accelerator and to polymerize to remove the heat of reaction in the presence of a low-boiling inert solvent which evaporates under reaction conditions (cf. U.S. Patents 3,129,2O5, 2,9O6,798, 4,391,959, EP-A1-154164, DE Patent 1O 99 171 and EP-B1-2553O). In the known methods, the evaporated solvent is compressed in a compressor and returned to the polymerization process.
Es hat sich nun gezeigt, daß Verunreinigungen im Isobutylen den Polymerisationsablauf empfindlich stören können. Aufgrund der physikalischen Daten (Kp 76O mm - 6,9°C, Fp: -14O°C) und der Herstellungsbedingungen enthält Isobutylen viele Verunreinigungen im Bereich von C₂- bis C₇-Kohlenwasserstoffen. Besonders im Bereich der C₄-Kohlenwasserstoffe gibt es eine größere Anzahl polymerisationsaktiver Komponente, die über eine sorgfältige Druckdestillation abgetrennt werden müssen.It has now been shown that impurities in the isobutylene can significantly interfere with the polymerization process. Due to the physical data (bp 76O mm - 6.9 ° C, mp: -14O ° C) and the manufacturing conditions, isobutylene contains many impurities in the range of C₂ to C₇ hydrocarbons. Especially in the field of C₄ hydrocarbons there are a large number of polymerization-active components that have to be separated by careful pressure distillation.
Während man für die Herstellung von niedermolekularen Polyisobutylenen C₄-Kohlenwasserstoff-Fraktionen verwenden kann, die neben Isobutylen noch n-Butan, Isobutan und n-Butene enthalten, werden an das Isobutylen für die Herstellung hochmolekularer und festen Polyisobutylene höhere Anforderungen gestellt. Das aus Isobutanol gewonnene und mit Normalbutenen, Isobutyraldehyd und Isobutyräther verunreinigte Spaltisobutylen (Reinheit ca. 88 - 99,8 Vol.-%) wirdhier zu einer sorgfältigen Destillation unterworfen. Nach der fraktionierten Destillation steht zwar ein hochwertiges Isobutylen zur Verfügung, das aber noch eine Reihe schwer abtrennbarer Störkomponenten enthält (Butadien-1.3, Propen, Isobutan, Buten-1). Die Konzentration der einzelnen Störkomponenten ist vom Spaltergebnis abhängig und kann deshalb nicht von vornherein spezifiziert oder definiert werden.While one can use C₄ hydrocarbon fractions for the production of low molecular weight polyisobutylenes, which contain n-butane, isobutane and n-butenes in addition to isobutylene, higher demands are placed on isobutylene for the production of high molecular weight and solid polyisobutylenes. The isobutylene obtained from isobutanol and contaminated with normal butenes, isobutyraldehyde and isobutyrether (purity approx. 88 - 99.8% by volume) is subjected to careful distillation here. After the fractional distillation, a high-quality isobutylene is available, but it still contains a number of difficult-to-separate interfering components (1,3-butadiene, propene, isobutane, butene-1). The concentration of the individual interference components depends on the cleavage result and therefore cannot be specified or defined from the outset.
Bei der Isolierung von Isobutylen aus C₄-Kohlenwasserstoffschnitten über Veretherung mit Methanol (MTBE) oder Isobutanol (IBTBE) und nachfolgender Spaltstufe des betreffenden Ethers entsteht ein Budimatisobutylen (Reinheit 99,98 - 99 Vol.-%), das fast frei von vorgenannten Störkomponenten ist. Während die Konzentration der für die Isobutylenpolymerisation störenden Komponenten im Spaltisobutylen zwischen O,2 - 12 Vol.-% liegen kann, ist bei Budimatisobutylen diese Konzentration auf < 2OOO Vol.-ppm begrenzt.When isolating isobutylene from C₄ hydrocarbon cuts via etherification with methanol (MTBE) or isobutanol (IBTBE) and the subsequent cleavage stage of the ether in question, a budimatisobutylene (purity 99.98 - 99 vol .-%) is formed, which is almost free of the aforementioned interfering components . While the concentration of the components which interfere with the isobutylene polymerization in the gap isobutylene can be between 0.2 and 12 vol.%, In budimatisobutylene this concentration is limited to <2OOO vol. Ppm.
Es hat sich nun gezeigt, daß das im Kreis geführte Lösungsmittel sowohl bei Verwendung von Spaltisobutylen als auch beim Einsatz von Budimatisobutylen nach kurzer Zeit eine so hohe Konzentration an Fremdstoffen, welche die Reglerwirkung stören und eine Erhöhung der Polymerisationszeit und des Katalysatorverbrauchs verursachen, mit sich führt, daß die Kreisgasleitungen sich mit nieder- bis mittelmolekularen Polyisobutylenen belegen und damit eine kontinuierliche Fahrweise verhindern.It has now been shown that the circulated solvent, both with the use of split isobutylene and with the use of budimatisobutylene, leads to such a high concentration of foreign substances after a short time, which disrupt the regulator action and cause an increase in the polymerization time and the catalyst consumption that the circulating gas lines are occupied with low to medium molecular weight polyisobutylenes and thus prevent a continuous driving style.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren aufzufinden, bei dem obenerwähnte Nachteile nicht auftreten und eine Umsatzsteigerung erreicht werden kann.The invention has for its object to find a method in which the above-mentioned disadvantages do not occur and an increase in sales can be achieved.
Diese Aufgabe wird erfindungsgemäß durch Verfahren gemäß Patentansprüche 1 bis 3 gelöst.This object is achieved according to the invention by methods according to claims 1 to 3.
Verfahren zur Herstellung von Polyisobutylen durch Polymerisation von Isobutylen in einer Polymerisationszone sind seit geraumer Zeit bekannt und werden in der Monographie von H. Güterbock "Chemische Technologie der Kunststoffe in Einzeldarstellungen, Polyisobutylen", 1959, Seiten 77 bis 1O5, Springer-Verlag, Berlin/Göttingen/Heidelberg ausführlich beschrieben. Die erhaltenen Polyisobutylene sind bei Raumtemperatur, je nach Molekulargewicht, viskos-ölig bis gummielastisch, haben eine Dichte von O,83 bis O,93 g/cm³ und weisen die Formel:
Die Polymerisation des Isobutylens erfolgt nach bekanntem Verfahren bei Reaktionstemperaturen zwischen O und -16O°C, vorzugsweise arbeitet man bei Temperaturen zwischen -5O°C und -11O°C. Das Verfahren arbeitet drucklos.The polymerization of isobutylene is carried out according to a known method at reaction temperatures between 0 and -16O ° C, preferably at temperatures between -5O ° C and -11O ° C. The process works without pressure.
Für das bekannte Verfahren verwendet man in erster Linie Bortrifluorid als Friedel-Crafts-Katalysator in üblichen Mengen von O,O1 bis 1,O Gewichtsprozent, bezogen auf das eingesetzte Isobutylen. Um bei einer gegebenen Temperatur das Molekulargewicht des Polyisobutylens gezielt einstellen zu können, bedient man sich gegebenenfalls der sogenannten Molekulargewichtsregler in üblichen Mengen von von 1 bis 5OOO Gew.-ppm, bezogen auf das eingesetzte Isobutylen. Derartige Molekulargewichtsregler sind beispielsweise die Verbindungen Diisobutylen, Mercaptane, Sulfide oder Polysulfide. Neben einer Erniedrigung des Molekulargewichts der entstehenden Isobutylenpolymerisate bewirken die Molekulargewichtsregler eine beträchtliche Erhöhung der Reaktionszeit und erfordern häufig auch eine Erhöhung des Katalysatorbedarfs.For the known process, primarily boron trifluoride is used as the Friedel-Crafts catalyst in customary amounts of from 0.01 to 1.0 percent by weight, based on the isobutylene used. In order to be able to adjust the molecular weight of the polyisobutylene at a given temperature, the so-called molecular weight regulators are used in customary amounts of from 1 to 50,000 ppm by weight, based on the isobutylene used. Such molecular weight regulators are, for example, the compounds diisobutylene, mercaptans, sulfides or polysulfides. In addition to lowering the molecular weight of the isobutylene polymers formed, the molecular weight regulators bring about a considerable increase in the reaction time and often also require an increase in the catalyst requirement.
Die Polymerisation des Isobutylens wird in Gegenwart von 1O bis 5OOO Gew.-ppm, bezogen auf das eingesetzte Isobutylen, eines Polymerisationsbeschleunigers durchgeführt. Diese Substanzen bewirken eine Beschleunigung des Reaktionsablaufs und eine Verringerung der erforderlichen Katalysatormenge. Als Folge dieser Zusätze entstehen außerdem hochmolekulare Polyisobutylene, da kettenabbrechende Einflüsse weniger wirksam werden. Es handelt sich hierbei vorzugsweise um primäre oder sekundäre Alkohole mit 1 bis 1O Kohlenstoffatomen, beispielsweise um Methanol, Äthanol, n-Propanol, iso-Propanol, n-Butanol, iso-Butanol, Amylalkohole, Cyclohexanol und Benzylalkohol. In Betracht kommen außerdem Phenole, Carbonsäuren oder Mineralsäuren.The polymerization of the isobutylene is carried out in the presence of 10 to 5,000 ppm by weight, based on the isobutylene used, of a polymerization accelerator. These substances accelerate the course of the reaction and reduce the amount of catalyst required. As a result of these additives, high-molecular polyisobutylenes are also formed, since chain-breaking influences are less effective. These are preferably primary or secondary alcohols with 1 to 10 carbon atoms, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, amyl alcohols, Cyclohexanol and benzyl alcohol. Phenols, carboxylic acids or mineral acids are also suitable.
Die Polymerisation des Isobutylens wird in Gegenwart von 3O bis 9O Gew.-%, bezogen auf das eingesetzte Isobutylen, eines unter Reaktionsbedingungen inerten, niedrigsiedenden Lösungsmittels vorgenommen. Wegen der günstigen Lage ihrer Siedepunkte geeignete Lösungsmittel sind bevorzugt Methan, Äthan, Propan und besonders Ethylen, da durch Verdampfen derselben unter Reaktionsbedingungen die Polymerisationswärme des Isobutylens auf einfache Weise abgeführt werden kann. Bei Verwendung der obengenannten Lösungsmittel, die gleichzeitig Kühlmittel sind, z.B. beim Einsatz von Ethylen, wird das Isobutylen bei Siedetemperatur des inerten Lösungsmitels polymerisiert. Im Falle des Ethylens beträgt die Polymerisationstemperatur -1O4°C.The polymerization of the isobutylene is carried out in the presence of 30 to 90% by weight, based on the isobutylene used, of a low-boiling solvent which is inert under the reaction conditions. Suitable solvents because of the favorable location of their boiling points are preferably methane, ethane, propane and especially ethylene, since the heat of polymerization of isobutylene can be removed in a simple manner by evaporating them under reaction conditions. When using the above solvents, which are also coolants, e.g. when using ethylene, the isobutylene is polymerized at the boiling point of the inert solvent. In the case of ethylene, the polymerization temperature is -1O4 ° C.
Nach bekannten Verfahren wird das bei der Polymerisation verdampfte Lösungsmittel kontinuierlich abgezogen, verflüssigt und in flüssigem Zustand erneut der Polymerisationszone zugeführt.According to known processes, the solvent evaporated during the polymerization is continuously drawn off, liquefied and returned to the polymerization zone in the liquid state.
Nach erfindungsgemäßem Verfahren wird in dem zu Polymerisation gelangenden monomeren Isobutylen ein Gehalt von 1,9 bis 2,1, bevorzugt 2,O Gew.-%, von Buten-1 konstant gehalten. Das Buten-1 ist in hoher Reinheit (99,3 Gew.-% Buten-1, O,2 Gew.-% Isobuten, O,4 Gew.-% Butan) auf dem Markt erhältlich und wird in dieser Form verwendet. Nach bevorzugter Verfahrensweise soll das Buten-1 in der Summe weniger als 5O Gew.-ppm cis-Buten-2 und trans-Buten-2 enthalten. Die cis- und trans-Isomere des Butens-2 müssen durch eine Druckdestillation sorgfältig abgetrennt und eine Trocknung mit Chlorcalcium durchgeführt werden. Das Buten-1 kann dem Isobutylen volumetrisch zugefügt werden. Wenn aufgrund der Herstellungsbedingungen schon gewisse Buten-1-Konzentrationen vorhanden sein sollten, ist entweder durch Zugabe von Buten-1 oder durch Zugabe von Reinstisobuten der Gehalt von Buten-1 auf 1,9 bis 2,1 bevorzugt 2,O Gew.%, einzustellen.According to the process of the invention, a content of 1.9 to 2.1, preferably 2.0,% by weight of butene-1 is kept constant in the monomeric isobutylene which is being polymerized. Butene-1 is available on the market in high purity (99.3% by weight of butene-1, 0.2% by weight of isobutene, 0.4% by weight of butane) and is used in this form. According to a preferred procedure, the butene-1 should contain a total of less than 50 ppm by weight of cis-butene-2 and trans-butene-2. The cis and trans isomers of butene-2 must be carefully separated by pressure distillation and dried with chlorine calcium. Butene-1 can be volumetrically added to the isobutylene. If certain butene-1 concentrations should already be present due to the production conditions, the content of butene-1 to 1.9 to 2.1 is preferably 2.0% by weight, either by adding butene-1 or by adding pure isobutene. adjust.
Die mit der Erfindung erzielten Vorteile sind insbesondere darin zu sehen, daß das Konstanthalten von ca. 2 Gew.-% der Reinsubstanz Buten-1 im Isobutylen das Polymerisationsverhalten des Isobutylen, wie Umsatzsteigerung, ruhiger Polymerisationsverlauf, reduzierte Katalysator- und Reglerkonzentration, verbessert.The advantages achieved with the invention are to be seen in particular in that keeping approximately 2% by weight of the pure substance butene-1 in the isobutylene improves the polymerization behavior of the isobutylene, such as an increase in turnover, a smooth polymerization process, a reduced catalyst and regulator concentration.
Das erfindungsgemäße Verfahren wird anhand der folgenden Beispiele näher erläutert. Die in den Beispielen angegebenen Molekulargewichte wurden nach Staudinger aus Viskositätsmessungen an verdünnten Polymerlösungen ermittelt. Um den Stand der Technik zu zeigen, wurde ein Spaltisobutylen mit variablem Buten-1-Gehalt und ein Budimatisobutylen mit O,O5 Gew.-% Buten-1 benutzt.The process according to the invention is explained in more detail with reference to the following examples. The molecular weights given in the examples were according to Staudinger from viscosity measurements on dilute polymer solutions. To show the state of the art, a split isobutylene with variable butene-1 content and a budimatisobutylene with 0.05% by weight of butene-1 were used.
Es ist bekannt, aus primären, sekundären und tertiären Alkoholen durch Überleiten der Alkoholdämpfe über Katalysatoren bei Temperaturen von 3OO° bis 45O°C Wasser abzuspalten und auf diese Weise Olefine herzustellen. Als Katalysatoren verwendet man γ-Aluminiumoxide (vgl. Houben-Weyl, Methoden der organischen Chemie, Bd. IV, Teile 2 [1955], Seite 21O). Die Dehydratisierungsprodukte sind in nachfolgender Tabelle zusammengefaßt und zeigen je nach Ausgangsstoff und Katalysator unterschiedliche Buten-1-Gehalte.
Die Arbeitstemperatur betrug jeweils etwa 31O°C.The working temperature was about 31O ° C.
Die in Versuch 1, 2, 3 und 4 erhaltenen Isobutylene wurden wie folgt untersucht:The isobutylenes obtained in experiments 1, 2, 3 and 4 were examined as follows:
Unter Ausschluß von Feuchtigkeit mischt man bei einer Temperatur von -7°C 12 g reines, getrocknetes, flüssiges Isobutylen gemäß Versuch 1 (bzw. 2, 3 + 4) mit 1OOO Gew.-ppm Isobutanol, bezogen auf das eingesetzte Isobutylen und 23 g reines, getrocknetes, flüssiges Ethen von -1O4°C.In the absence of moisture, 12 g of pure, dried, liquid isobutylene according to experiment 1 (or 2, 3 + 4) are mixed with 100% by weight ppm isobutanol, based on the isobutylene used, and 23 g at a temperature of -7 ° C. pure, dried, liquid ethene at -1O4 ° C.
1OO mg Bortrifluorid (Reinheit größer als 99,7 Vol.-%) werden in 23 g reinem, getrocknetem, flüssigen Ethen von -1O4°C gelöst.100 mg of boron trifluoride (purity greater than 99.7% by volume) are dissolved in 23 g of pure, dried, liquid ethene at -1O4 ° C.
Die Katalysatorlösung wird der Polymerisationslösung zuaddiert. Die Reaktion verläuft unter Aufsieden und Verdampfen des Ethens und ist nach den in der Tabelle angegebenen Reaktionszeiten beendet.
Dem Isobutylen aus Versuch 4 werden die in der Tabelle angegebenen Buten-1-Konzentrationen addiert und wie oben beschrieben untersucht. Das Buten-1 hat folgende Reinheit: 99,7 Gew.-% Buten-1, O,2 Gew.-% Butan (n- und Isobutan), Summe von cis- und trans-Buten-2 5O Gew.-ppm, Rest Isobutylen.
Die Mischung: 98 Gew.-% Reinstisobutylen (99,99 Gew.-% Isobutylen, < 1OO Gew.-ppm Butan, < 5O Gew.-ppm cis- und trans-Buten-2) und 2 Gew.-% n-Buten-1 stellt die optimalste Bedingung dar.The mixture: 98% by weight pure isobutylene (99.99% by weight isobutylene, <100% by weight butane, <50% by weight cis and trans-butene-2) and 2% by weight n- Butene-1 is the most optimal condition.
Während bei der Dehydratisierung von Isobutanol ein Isobutylen - je nach Verfahrensbedingungen - mit variablem Buten-1-Gehalt anfällt, entsteht bei der Dehadratisierung von Tertiärbutylalkohol ein Reinstisobutylen (99,99 Gew.-% Reinheit) mit geringstem Buten-1 Gehalt. Eine Destillation kann das Buten-1 von Isobutylen nicht abtrennen, da die Siedepunkte zu nahe beieinander liegen (Kp von Isobutylen -6,9°C; Kp von Buten-1 -6, 26°C). Für eine störungsfreie Isobutylenpolymerisation zur Erzielung hochmolekularer Polyisobutylene ist aber ein Isobutylen mit konstantem Buten-1-Gehalt von 1,9 bis 2,1, insbesondere 2,O Gew.% erforderlich.While the dehydration of isobutanol produces an isobutylene - depending on the process conditions - with a variable butene-1 content, the dehadration of tertiary butyl alcohol produces a pure isobutylene (99.99% by weight purity) with the lowest butene-1 content. Distillation cannot separate butene-1 from isobutylene because the boiling points are too close to each other (bp of isobutylene -6.9 ° C; bp of butene-1 -6, 26 ° C). For trouble-free isobutylene polymerization to achieve high molecular weight polyisobutylenes, however, an isobutylene with a constant butene-1 content of 1.9 to 2.1, in particular 2.0% by weight, is required.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86110542T ATE63320T1 (en) | 1985-08-01 | 1986-07-30 | PROCESS FOR POLYMERIZATION OF ISOBUTYLENE. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3527551 | 1985-08-01 | ||
| DE19853527551 DE3527551A1 (en) | 1985-08-01 | 1985-08-01 | METHOD FOR POLYMERIZING ISOBUTYLENE |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0213401A2 true EP0213401A2 (en) | 1987-03-11 |
| EP0213401A3 EP0213401A3 (en) | 1989-06-14 |
| EP0213401B1 EP0213401B1 (en) | 1991-05-08 |
Family
ID=6277353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86110542A Expired - Lifetime EP0213401B1 (en) | 1985-08-01 | 1986-07-30 | Process for the polymerization of isobutylene |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4691072A (en) |
| EP (1) | EP0213401B1 (en) |
| AT (1) | ATE63320T1 (en) |
| DE (2) | DE3527551A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0742234A1 (en) * | 1995-05-11 | 1996-11-13 | Institut Francais Du Petrole | Process and installation for the conversion of the olefinic C4-cut into polyisobutene and propylene |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4982026A (en) * | 1987-07-30 | 1991-01-01 | The Lubrizol Corporation | Lower alkene polymers |
| US4973789A (en) * | 1987-07-30 | 1990-11-27 | The Lubrizol Corporation | Lower alkene polymers |
| US5268520A (en) * | 1987-07-30 | 1993-12-07 | The Lubrizol Corporation | Lower alkene polymers |
| US5017279A (en) * | 1988-12-29 | 1991-05-21 | Exxon Research And Engineering Company | Multistep process for the manufacture of novel polyolefin lubricants from sulfur containing thermally cracked petroleum residua |
| DE4231748A1 (en) * | 1992-09-23 | 1994-03-24 | Basf Ag | Process for regulating the reaction in the production of polyisobutylene |
| US5414179A (en) * | 1994-04-29 | 1995-05-09 | Phillips Petroleum Company | Method for controlling the feed composition to a process for polymerizing isobutylene |
| CA2385576C (en) | 1999-09-16 | 2012-05-01 | Texas Petrochemicals Lp | Process for preparing polyolefin products |
| US6884858B2 (en) | 1999-10-19 | 2005-04-26 | Texas Petrochemicals Lp | Process for preparing polyolefin products |
| US6562913B1 (en) | 1999-09-16 | 2003-05-13 | Texas Petrochemicals Lp | Process for producing high vinylidene polyisobutylene |
| US6858188B2 (en) | 2003-05-09 | 2005-02-22 | Texas Petrochemicals, Lp | Apparatus for preparing polyolefin products and methodology for using the same |
| US7037999B2 (en) * | 2001-03-28 | 2006-05-02 | Texas Petrochemicals Lp | Mid-range vinylidene content polyisobutylene polymer product and process for producing the same |
| US6992152B2 (en) * | 1999-10-19 | 2006-01-31 | Texas Petrochemicals Lp | Apparatus and method for controlling olefin polymerization process |
| US20100298507A1 (en) * | 2009-05-19 | 2010-11-25 | Menschig Klaus R | Polyisobutylene Production Process With Improved Efficiencies And/Or For Forming Products Having Improved Characteristics And Polyisobutylene Products Produced Thereby |
| KR20200030561A (en) | 2017-07-13 | 2020-03-20 | 아란세오 도이치란드 게엠베하 | Method for preparing isobutene polymer using improved temperature control |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1447837A (en) * | 1964-09-28 | 1966-07-29 | Eastman Kodak Co | Process for preparing polymers of regular molecular mass |
| FR2147263A1 (en) * | 1971-07-27 | 1973-03-09 | Nat Petro Chem | |
| EP0025530A2 (en) * | 1979-09-08 | 1981-03-25 | BASF Aktiengesellschaft | Process for the production of polyisobutenes |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE497299A (en) * | 1949-09-30 | |||
| US2775577A (en) * | 1952-12-23 | 1956-12-25 | Exxon Research Engineering Co | Controlled isobutylene polymerization |
| US2906798A (en) * | 1957-08-28 | 1959-09-29 | Gulf Research Development Co | Hydroisomerization process and apparatus |
| US2918508A (en) * | 1957-12-02 | 1959-12-22 | Standard Oil Co | Polyisobutylene production |
| US3129205A (en) * | 1958-11-03 | 1964-04-14 | Exxon Research Engineering Co | Reactor flushing system |
| DE3010870A1 (en) * | 1980-03-21 | 1981-10-01 | Basf Ag, 6700 Ludwigshafen | METHOD FOR POLYMERIZING ISOBUTYLENE |
| GB8329082D0 (en) * | 1983-11-01 | 1983-12-07 | Bp Chem Int Ltd | Low molecular weight polymers of 1-olefins |
-
1985
- 1985-08-01 DE DE19853527551 patent/DE3527551A1/en not_active Withdrawn
-
1986
- 1986-07-22 US US06/887,938 patent/US4691072A/en not_active Expired - Lifetime
- 1986-07-30 EP EP86110542A patent/EP0213401B1/en not_active Expired - Lifetime
- 1986-07-30 DE DE8686110542T patent/DE3679121D1/en not_active Expired - Lifetime
- 1986-07-30 AT AT86110542T patent/ATE63320T1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1447837A (en) * | 1964-09-28 | 1966-07-29 | Eastman Kodak Co | Process for preparing polymers of regular molecular mass |
| FR2147263A1 (en) * | 1971-07-27 | 1973-03-09 | Nat Petro Chem | |
| EP0025530A2 (en) * | 1979-09-08 | 1981-03-25 | BASF Aktiengesellschaft | Process for the production of polyisobutenes |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0742234A1 (en) * | 1995-05-11 | 1996-11-13 | Institut Francais Du Petrole | Process and installation for the conversion of the olefinic C4-cut into polyisobutene and propylene |
| FR2733986A1 (en) * | 1995-05-11 | 1996-11-15 | Inst Francais Du Petrole | PROCESS AND INSTALLATION FOR THE CONVERSION OF OLEFINIC C4 CUTS INTO POLYISOBUTENES AND PROPYLENE |
| US5877365A (en) * | 1995-05-11 | 1999-03-02 | Institut Francais Du Petrole | Process and plant for the conversion of olefinic C4 cuts to polyisobutene and to propylene |
| US6207115B1 (en) | 1995-05-11 | 2001-03-27 | Institut Francais Du Petrole | Process and plant for the conversion of olefinic C4 cuts to polyisobutene and to propylene |
Also Published As
| Publication number | Publication date |
|---|---|
| US4691072A (en) | 1987-09-01 |
| EP0213401B1 (en) | 1991-05-08 |
| ATE63320T1 (en) | 1991-05-15 |
| DE3679121D1 (en) | 1991-06-13 |
| EP0213401A3 (en) | 1989-06-14 |
| DE3527551A1 (en) | 1987-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0213401B1 (en) | Process for the polymerization of isobutylene | |
| EP0628575B1 (en) | Process for the manufacture of highly reactive polyisobutenes | |
| EP1040143B1 (en) | Method for producing low-molecular, highly reactive polyisobutylene | |
| EP1095070B1 (en) | Method for producing highly reactive polyisobutenes | |
| EP0807641B1 (en) | Process for the preparation of medium molecular highly reactive polyisobutene | |
| EP3599230B1 (en) | Method for the oligomerization of butene by detecting the proportion of acid catalysis | |
| WO2002006359A1 (en) | Method for producing polyisobutylenes | |
| WO2007141277A1 (en) | Preparation of reactive, essentially halogen-free polyisobutenes from c4-hydrocarbon mixtures which are low in isobutene | |
| DD222000A5 (en) | METHOD OF RECOVERING BUTEN-1 OF THE POLYMERIZATION STAGE | |
| EP0036974B1 (en) | Process for the polymerization of isobutylene | |
| EP1117708B1 (en) | Method for producing halogen-free reactive polyisobutene | |
| EP0025530B1 (en) | Process for the production of polyisobutenes | |
| EP2814852A1 (en) | Boron trifluoride catalyst complex and method for producing highly reactive isobutene homopolymers | |
| WO1999007753A1 (en) | Process for preparing halogen-free, reactive polyisobutylene | |
| EP0154164B1 (en) | Process for the polymerisation of isobutylene | |
| DE2061289C3 (en) | ||
| WO2005066222A1 (en) | Production of highly reactive polyisobutenes with a low fluorine content by means of a moderator | |
| DE2160465A1 (en) | Process for the production of p-tert. Butyl phenol | |
| DE3510764C2 (en) | Process for the preparation of isobutene | |
| EP2097460B1 (en) | Method for the removal of isobutene oligomers from an isobutene polymer | |
| DE10361638A1 (en) | Production of polyisobutene, used e.g. as intermediate for lubricating oil and fuel additives, involves polymerization using boron trifluoride catalyst with cyanide or nitrile as moderator and/or contacting product with inorganic adsorbent | |
| DE3520291A1 (en) | METHOD FOR THE CATALYTIC CRACKING OF LIGHT DISTILLATES | |
| EP4368603A1 (en) | Process for producing olefins from oxygenates with variable production of ethylene and propylene | |
| DE659470C (en) | Process for the production of high molecular weight polymerization products of isobutylene | |
| AT208826B (en) | Process for isomerizing an isomerizable saturated hydrocarbon fraction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE DE FR GB NL |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE DE FR GB NL |
|
| 17P | Request for examination filed |
Effective date: 19890511 |
|
| 17Q | First examination report despatched |
Effective date: 19900911 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE DE FR GB NL |
|
| REF | Corresponds to: |
Ref document number: 63320 Country of ref document: AT Date of ref document: 19910515 Kind code of ref document: T |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
| REF | Corresponds to: |
Ref document number: 3679121 Country of ref document: DE Date of ref document: 19910613 |
|
| ET | Fr: translation filed | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19990618 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19990628 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19990630 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19990714 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19990716 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19990722 Year of fee payment: 14 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES Effective date: 20000714 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000730 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000730 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000731 |
|
| BERE | Be: lapsed |
Owner name: BASF A.G. Effective date: 20000731 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010201 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20000730 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010330 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20010201 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |